Hydrocarbons are found in a variety of gases, such as natural gas, refinery gas, and synthetic gas streams obtained from other hydrocarbon materials such as coal, crude oil, naphtha, oil shale, tar sands, and lignite. The hydrocarbon constituents of natural gas usually have a major proportion of methane and ethane, i.e., methane and ethane together comprise at least 50 mole percent of the total hydrocarbon components. The gas also usually contains relatively lesser amounts of heavier hydrocarbons such as propane, butanes, pentanes, and the like, as well as carbon dioxide, hydrogen, nitrogen, and other gases.
In many cases, the gas streams from these sources are contaminated with high concentrations of carbon dioxide, making the gas streams unsuitable for use as fuel, chemical plant feedstock, or other purposes. There are a variety of processes that have been developed to remove the carbon dioxide using chemical, physical, and hybrid solvents. Other processes have been developed that use a refrigerated absorbent stream composed of heavy (C4-C10 typically) hydrocarbons to remove the carbon dioxide in a distillation column, such as the process described in U.S. Pat. No. 4,318,723. All of these processes have increasingly higher capital cost and operating cost as the carbon dioxide concentration in the gas stream increases, which often makes processing of such gas streams uneconomical.
One method for improving the economics of processing gas streams containing high concentrations of carbon dioxide is to provide bulk separation of the carbon dioxide from the gas stream prior to processing with solvents or absorbents, so that only a minor fraction of the carbon dioxide must then be removed from the gas stream. For example, semi-permeable membranes have often been used for bulk removal of carbon dioxide. However, a significant fraction of the lighter hydrocarbons in the gas stream are often “lost” in the carbon dioxide stream that is separated by bulk removal processes of this type.
A better alternative for bulk removal of carbon dioxide is to use distillation to fractionate the gas stream into a light hydrocarbon stream and a carbon dioxide stream, so that removal of the residual carbon dioxide from the light hydrocarbon stream is all that is required to produce pipeline-quality gas for use as fuel, chemical plant feedstock, etc. The majority of the carbon dioxide that is removed is recovered as a liquid rather than a vapor, allowing the carbon dioxide to be pumped (rather than compressed) for subsequent use in tertiary oil recovery operations or for other purposes, resulting in substantial reductions in capital cost and operating cost.
The present invention is generally concerned with the removal of the majority of the carbon dioxide from such gas streams. A typical analysis of a gas stream to be processed in accordance with this invention would be, in approximate mole percent, 31.0% methane, 0.4% ethane and other C2 components, 0.1% propane and other C3 components, 0.1% butanes plus, and 67.7% carbon dioxide, with the balance made up of nitrogen. Sulfur containing gases are also sometimes present.
In a typical distillation process for removing carbon dioxide, a feed gas stream under pressure is cooled by heat exchange with other streams of the process and/or external sources of refrigeration such as a Freon compression-refrigeration system. The gas is condensed as it is cooled, and the high-pressure liquid is expanded to an intermediate pressure, resulting in further cooling of the stream due to the vaporization occurring during expansion of the liquids. The expanded stream, comprising a mixture of liquid and vapor, is fractionated in a distillation column to separate residual methane, nitrogen, and other volatile gases as overhead vapor from the carbon dioxide and the heavier hydrocarbon components as bottom liquid product. A portion of the liquid carbon dioxide can be flash expanded to lower pressure and thereafter used to provide low level refrigeration to the process streams if desired.
The present invention employs a novel means of performing the various steps described above more efficiently and using fewer pieces of equipment. This is accomplished by combining what heretofore have been individual equipment items into a common housing, thereby reducing the plot space required for the processing plant and reducing the capital cost of the facility. Surprisingly, applicants have found that the more compact arrangement also reduces the power consumption required to achieve a given level of carbon dioxide removal, thereby increasing the process efficiency and reducing the operating cost of the facility. In addition, the more compact arrangement also eliminates much of the piping used to interconnect the individual equipment items in traditional plant designs, further reducing capital cost and also eliminating the associated flanged piping connections. Since piping flanges are a potential leak source for carbon dioxide (a greenhouse gas) and for hydrocarbons (which are volatile organic compounds, VOCs, that contribute to greenhouse gases and may also be precursors to atmospheric ozone formation), eliminating these flanges reduces the potential for atmospheric emissions that can damage the environment.
In accordance with the present invention, it has been found that more than 87% of the carbon dioxide can be removed while leaving more than 99% of the methane in the residue gas stream. The present invention, although applicable at lower pressures and warmer temperatures, is particularly advantageous when processing feed gases in the range of 400 to 1500 psia [2,758 to 10,342 kPa(a)] or higher under conditions requiring distillation column overhead temperatures of −50° F. [−46° C.] or colder.
In the following explanation of the above figures, tables are provided summarizing flow rates calculated for representative process conditions. In the tables appearing herein, the values for flow rates (in moles per hour) have been rounded to the nearest whole number for convenience. The total stream rates shown in the tables include all non-hydrocarbon components and hence are generally larger than the sum of the stream flow rates for the hydrocarbon components. Temperatures indicated are approximate values rounded to the nearest degree. It should also be noted that the process design calculations performed for the purpose of comparing the processes depicted in the figures are based on the assumption of no heat leak from (or to) the surroundings to (or from) the process. The quality of commercially available insulating materials makes this a very reasonable assumption and one that is typically made by those skilled in the art.
For convenience, process parameters are reported in both the traditional British units and in the units of the Système International d'Unités (SI). The molar flow rates given in the tables may be interpreted as either pound moles per hour or kilogram moles per hour. The energy consumptions reported as horsepower (HP) and/or thousand British Thermal Units per hour (MBTU/Hr) correspond to the stated molar flow rates in pound moles per hour. The energy consumptions reported as kilowatts (kW) correspond to the stated molar flow rates in kilogram moles per hour.